4- and 5-substituted 1,2,3-triazole, and regioisomer mixtures thereof, modified polymers

ABSTRACT

Provided are novel 4- and 5-substituted 1,2,3-triazoles, and regioisomer mixtures thereof, modified polymers, wherein the substituted 1,2,3-triazoles are modified by reaction with a modifying polymer (maleic anhydride based polymer). Depending upon the ratio of the substituted 1,2,3-triazole to the maleic anhydride based polymer employed, the resulting modified polymers can provide maleic anhydride based polymers that are partially or fully reacted with the substituted 1,2,3-triazoles. The resulting modified polymers may be partially or fully opened to provide amic acids, carboxylic acids, carboxylic acidic salts, imides, or esters. The novel 4- or 5-substituted 1,2,3-triazoles, and regioisomer mixtures thereof, modified polymers can be converted to a wide variety of useful polymers and may be employed in a wide variety of compositions. An example of a modified polymer may be represented by the structure:formule: (1) wherein m, n, and q are defined herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Provided are novel 4- and 5-substituted 1,2,3-triazoles, and regioisomermixtures thereof, modified polymers, wherein the substituted1,2,3-triazoles are modified by reaction with a modifying polymer(maleic anhydride based polymer). Depending upon the ratio of thesubstituted 1,2,3-triazole to the maleic anhydride based polymeremployed, the resulting modified polymers can provide maleic anhydridebased polymers that are partially or fully reacted with the substituted1,2,3-triazoles. The resulting modified polymers may be partially orfully opened to provide amic acids, carboxylic acids, carboxylic acidicsalts, imides, esters, and mixtures thereof. The mixtures of 4- and5-substituted regioisomers of 1,2,3-triazoles may be used as mixtures ormay be separated to provide purified modified polymers. The novel 4- or5-substituted 1,2,3-triazoles, and regioisomer mixtures thereof,modified polymers can be converted to a wide variety of useful polymers.The novel modified polymers of the invention can be employed in a widevariety of compositions.

2. Description of Related Art

Reactions of maleic anhydride based polymers with amines and alcohols toprovide polymeric imides, amic acids, and maleic anhydride half estersand full esters are known, U.S. Pat. No. 6,025,501. These polymericproducts are particularly useful in pharmaceutical compositions andpersonal care compositions, such as hair care and skin care products.

Modification of 4- and 5-substituted 1,2,3-triazoles, and regioisomermixtures thereof, to provide modified polymers that result in adifference in the physical or mechanical properties of the polymerscould provide additional useful personal care and pharmaceuticalproducts. The resulting modification of the physical or mechanicalproperties would depend upon the type of the modifying polymer and the4- and 5-substituted 1,2,3-triazole employed.

Accordingly, there is a need for polymers resulting from modification of4- and 5-substituted 1,2,3-triazoles, and regioisomer mixtures thereof,with modifying maleic anhydride based polymers to alter or improve thephysical and mechanical properties of such polymers.

SUMMARY OF THE INVENTION

The invention provides 4- and 5-substituted 1,2,3-triazole, orregioisomer mixtures thereof, modified polymers, wherein the substituted1,2,3-triazole is modified by a modifying polymer represented by thestructure:

wherein R₁ is selected from the group consisting of hydrogen,functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl,and aryl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof.

Examples of modified polymers may be represented by the structures:

wherein R₁, R₂, and R₃ are each independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,alkoxy, cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof; M₁ is selected from the group consisting of hydrogen, alkalimetals, and alkaline earth metals; M₂ is an alkali metal or an alkalineearth metal; each m, n, and q is an integer independently ranging fromabout 2 to about 500; and each p is an integer independently rangingfrom 1 to about 50.

DETAILED DESCRIPTION

In one aspect, novel 4- and 5-substituted 1,2,3-triazoles, andregioisomer mixtures thereof, modified polymers are provided. Thesubstituted 1,2,3-triazoles are modified by reaction with a modifyingpolymer, such as a maleic anhydride based polymer. Depending upon theratio of the maleic anhydride based polymer to the substituted1,2,3-triazole employed, the resulting modified polymers can providemaleic anhydride based polymers that are partially or fully reacted withthe substituted 1,2,3-triazoles. The resulting modified polymers may bepartially or fully ring-opened to provide amic acids, carboxylic acids,carboxylic acidic salts, imides, esters, and mixtures thereof. Themixtures of 4- and 5-substituted regioisomers of 1,2,3-triazoles may beused as mixtures or may be separated to provide purified modifiedpolymers. The novel 4- and 5-substituted 1,2,3-triazoles, andregioisomer mixtures thereof, modified polymers can be converted to awide variety of useful polymers. The polymers may be random, blocked, oralternating polymers.

In another aspect, a wide variety of compositions comprising the novelmodified polymers are provided, including adhesives, aerosols,agricultural compositions, beverages, biocides, cleaning compositions,coating compositions, cosmetic compositions, dental compositions,detergents, drugs, electronics, encapsulations, foods, hair sprays,household-industrial-institutional (HI&I), inks, lithographic solutions,membrane compositions, metal fluids, oilfield compositions, paints,paper, personal care compositions, pharmaceuticals, plasters, plastics,printing, and wood-care compositions.

Personal care compositions refers to such illustrative non-limitingcompositions as cosmetics, drug delivery systems, hair, oil,pharmaceuticals, pigment dispersions, preservative compositions,including those to alter the color and appearance of the skin, skin,sun, and tissue regeneration scaffolds. Other personal care compositionsinclude, but are not limited to, modified natural oils for increasedflexibility in styling, durable styling, increased humidity resistancefor hair, skin, and color cosmetics, sun care water-proof/resistance,wear-resistance, shower gels, shampoos, and thermal protecting/enhancingcompositions. Dental personal care compositions include dentureadhesives, toothpastes, mouth washes, and the like. Pharmaceuticalcompositions include tablet coatings, tablet binders, transdermalpatches, and the like. The wide variety of compositions are describedbelow in detail.

In another embodiment, the invention provides 4- and 5-substituted1,2,3-triazoles, and regioisomer mixtures thereof, modified polymershaving a wide variety of physical and mechanical properties to suit aparticular application. The properties of the modified polymers can bedesigned by selecting the particular type of maleic anhydride basedpolymer and substituted 1,2,3-triazole employed, and by adjusting theratio of the maleic anhydride based polymer to the substituted1,2,3-triazole to partially or fully react the substituted1,2,3-triazole with the maleic anhydride based polymer. The propertiesof the modified polymers can be further designed by selecting the degreeand type of ring opening of the maleic anhydride based polymer topartially or fully react the maleic anhydride based polymer to provideamic acids, carboxylic acids, carboxylic acidic salts, imides, oresters. Appropriate selection of the types of polymers employed, theratios of the polymers and the degree and type of ring opening, can beused to provide the desired physical properties of the modified polymerincluding the hydrophilic, hydrophobic, and mechanical properties.

As used herein, the following terms have the meanings set out below.

The term “amic acid” refers to an organic compound that has both acarboxylic acid and an amide functional group. The nitrogen atom in theamide functional group may or may not be substituted with an organicfunctional group. Amic acids are also called carbamoyl carboxylic acids.

The term “are each independently selected from the group consisting of”means that when a group appears more than once in a structure, thatgroup may be independently selected each time it appears. For example,in the structure below:

R₁ and p each appear more than once. The term “are each independentlyselected from the group consisting of” means that each R₁ and p groupmay be the same or different.

The symbol of a “bond to the middle of a vinyl group” means that thebond can be attached to either side of the vinyl group and generallymeans that the structure is referring to a mixture of isomers. Forexample, in the structure below:

the vinyl group in the triazole moiety containing the

group can be attached to either the 4 or the 5 position of the1,2,3-triazole moiety. R₂, X, and p are defined below.

The term “branched and unbranched alkyl groups” refers to alkyl groups,which may be straight chained or branched. For example, the alkyl groupshave from 1 to about 18 carbon atoms, more particularly, from 1 to about10 carbon atoms, and yet more particularly from 1 to about 6 carbonatoms. Branched groups include isopropyl, tert-butyl, and the like.

The term “copolymer” refers to chains comprising more than one type ofmonomer unit.

The term “generic substituent(s)” refer(s) to substituent(s) such as R₁,R₂, R₃, M₁, M₂, m, n, and p, used and defined in the present invention.

The term “halogen” refers to chloro, bromo, iodo and fluoro, and in oneembodiment is bromo and/or chloro.

The term “heteroatom” refers to atoms such as oxygen, nitrogen, sulfur,and phosphorous. When the heteroatom is a nitrogen atom, the nitrogenatom may be present in the form of a quaternary amine.

The term “imide” refers to an organic compound comprising two carbonylgroups (acyl groups) bound to nitrogen atom. The nitrogen atom in theimide functional group may or may not be substituted with an organicfunctional group.

The term “inert solvent” refers to a solvent that does not interferechemically with the reaction.

The term “M₁” refers to hydrogen or an alkali metal or an alkaline earthmetal. The alkali metals comprise lithium, sodium, potassium, rubidium,caesium, and francium; in one embodiment, the alkali metal is lithium,sodium, or potassium. The alkaline earth metals comprise beryllium,magnesium, calcium, strontium, barium, and radium, in one embodiment,the alkaline earth metal is magnesium or calcium.

The term “M₂” refers to an alkali metal or an alkaline earth metal. Thealkali metals comprise lithium, sodium, potassium, rubidium, caesium,and francium; in one embodiment the alkali metal is lithium, sodium, orpotassium. The alkaline earth metals comprise beryllium, magnesium,calcium, strontium, barium, and radium, in one embodiment the alkalineearth metal is magnesium or calcium.

The term “modifying polymer” refers to a maleic anhydride based polymerrepresented by the structure:

wherein R₁ is defined herein.

The term “modified polymer” refers to a 4- or 5-substituted1,2,3-triazole, or regioisomer mixtures thereof, modified by a modifyingpolymer, as defined above. Illustrative non-limiting examples ofmodified polymers are set out above in the Summary of the Invention.

The term “monomer” refers to the repeat units comprising a polymer. Amonomer is a small molecule that chemically bonds to other monomers toform a polymer.

The term “non-homopolymer” refers to a polymer formed from two or moremonomers and includes essentially all polymers that are nothomopolymers. Nonlimiting examples of non-homopolymers includecopolymers, terpolymers, tetramers, and the like, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

The term “polymer” refers to a large molecule (macromolecule) composedof repeating structural units (monomers) connected by covalent chemicalbonds.

The term “polymerization” refers to methods for chemically reactingmonomer compounds to form polymer chains. The polymer chain may bealternating, blocked, or random. The type of polymerization method maybe selected from a wide variety of methods. Such methods include, butare not limited to, free radical polymerization methods, such asclassical radical polymerization and controlled radical polymerization,Nitroxide Mediation Polymerization (NMP), Atom Transfer RadicalPolymerization (ATRP), and Reversible Addition FragmentationChain-Transfer (RAFT).

The term “respectively” is a term that denotes that the items in a listcorrespond to each other in the order they are given. With reference totwo or more items, the term refers in a parallel or sequential manner.

The term “4- or 5-substituted 1,2,3-triazole, or regioisomer mixturesthereof” refers to 4-substituted 1,2,3-triazoles, 5-substituted1,2,3-triazoles, and 4- and 5-regioisomer mixtures of substituted1,2,3-triazoles, respectively. Some non-limiting examples of structuresof 4-substituted 1,2,3-triazoles include:

some non-limiting examples of 5-substituted 1,2,3-triazoles include:

and some non-limiting examples of 4- and 5-regioisomer mixtures ofsubstituted 1,2,3-triazoles include:

wherein R₂, X, and p are defined herein.

As set out above, provided are novel 4- and 5-substituted1,2,3-triazoles, and regioisomer mixtures thereof, modified polymers.The substituted 1,2,3-triazoles are modified by a modifying polymer,which is a maleic anhydride based polymer represented by the structure:

wherein R₁ is selected from the group consisting of hydrogen,functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl,and aryl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof. In one embodiment, R₁ isselected from the group consisting of hydrogen and functionalized andunfunctionalized alkyl and alkoxy groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof. More particularly, R₁ is selected from the group consisting offunctionalized and unfunctionalized alkyl and alkoxy groups.

The 4- and 5-substituted 1,2,3-triazoles, and regioisomer mixturesthereof, are represented by the structures, respectively:

Each X is OH or NHR₂. In one embodiment, each X is OH. Each R₂ isindependently selected from the group consisting of hydrogen,functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl,and aryl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof. In a separate embodiment,each R₂ is independently selected from the group consisting of hydrogenand functionalized and unfunctionalized alkyl and alkoxy groups, whereinany of the before mentioned groups may be with or without heteroatoms,and mixtures thereof. More particularly, each R₂ is independentlyselected from the group consisting of functionalized andunfunctionalized alkyl and alkoxy groups. Each p is an integerindependently ranging from 1 to about 50. In another embodiment, each pis an integer independently ranging from 1 to about 15. Moreparticularly, each p is an integer independently ranging from 1 to about6.

Examples of modified polymers according to the invention may berepresented by the structures:

R₁, R₂, and R₃ are each independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, alkoxy,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof. For example, in an embodiment, each R₁, R₂, and R₃ isindependently selected from the group consisting of hydrogen andfunctionalized and unfunctionalized alkyl and alkoxy groups, wherein anyof the before mentioned groups may be with or without heteroatoms, andmixtures thereof. More particularly, each R₁, R₂, and R₃ isindependently selected from the group consisting of functionalized andunfunctionalized alkyl and alkoxy groups. Each M₁ is independentlyselected from the group consisting of hydrogen, alkali metals, andalkaline earth metals. Each M₂ is independently an alkali metal or analkaline earth metal. Each m, n, and q is an integer independentlyranging from about 2 to about 500. In one aspect, each m, n, and q is aninteger independently ranging from about 2 to about 100. Moreparticularly, each m, n, and q is an integer independently ranging fromabout 2 to about 50. Each p is an integer independently ranging from 1to about 50, and particularly, each p is an integer independentlyranging from 1 to about 15. More particularly, each p is an integerindependently ranging from 1 to about 6.

In one embodiment, the modified polymer is represented by the structure:

wherein the generic substituents are defined above.

In another embodiment, the modified polymer is represented by thestructure:

wherein the generic substituents are defined above.

In another embodiment, the modified polymer is represented by thestructure:

wherein the generic substituents are defined above.

In another embodiment, the modified polymer is represented by thestructure:

wherein the generic substituents are defined above.

In yet another embodiment, the modified polymer is represented by thestructure:

wherein the generic substituents are defined above.

Depending on the end application, one or more fillers may be included inthe compositions and may be added for improved rheological propertiesand/or stress reduction. Examples of suitable nonconductive fillersinclude alumina, aluminum hydroxide, silica, fused silica, fumed silica,vermiculite, mica, wollastonite, calcium carbonate, titania, sand,glass, barium sulfate, zirconium, carbon black, organic fillers, andhalogenated ethylene polymers, such as, tetrafluoroethylene,trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidenechloride, and vinyl chloride. Examples of suitable conductive fillersinclude carbon black, graphite, gold, silver, copper, platinum,palladium, nickel, aluminum, silicon carbide, boron nitride, diamond,and alumina. Combinations of these fillers may be used.

The filler particles may be of any appropriate size, particularly fromthe nano to micro range. The choice of such size for any particular enduse is within the expertise of one skilled in the art. The filler may bepresent in an amount from about 10% to about 90% by weight of the totalcomposition. More than one filler type may be used in a composition andthe fillers may or may not be surface treated. Appropriate filler sizescan be determined by the practitioner, and, in particular, may be withinthe range from about 20 nm to about 100 μm.

Other materials, such as adhesion promoters (e.g. epoxides, silanes),dyes, pigments, and rheology modifiers may be added as desired for themodification of the final properties. Such materials and the amountsneeded are within the expertise of those skilled in the art.

Mixtures of 4- and 5-substituted regioisomers of 1,2,3-triazoles may beused as mixtures or may be separated, e.g., by chromatography, toprovide purified 4-substituted regioisomers and 5-substitutedregioisomers of the modified polymers. The novel 4- or 5-substituted1,2,3-triazoles, and regioisomer mixtures thereof, modified polymers canbe converted to a wide variety of useful polymers. The polymers may berandom, blocked, or alternating polymers. The novel modified polymers ofthe invention can be employed in a wide variety of compositions.

Chromatography is the collective term for a group of laboratorytechniques for the separation of mixtures. The techniques involvepassing a mixture dissolved in a mobile phase through a stationaryphase, which separates the analyte to be measured from other moleculesin the mixture and allows it to be isolated. Preparative chromatography,one particular technique, separates the components of a mixture forfurther use and is a form of purification. The various forms ofchromatography are well known to those of skill in the art.

The most general technique for separating large amounts of material iscolumn chromatography. Column chromatography is a separation techniquein which the stationary bed is within a tube. The particles of the solidstationary phase or the support coated with a liquid stationary phasemay fill the whole inside volume of the tube (packed column) or beconcentrated on or along the inside tube wall leaving an open,unrestricted path for the mobile phase in the middle part of the tube.Differences in rates of movement through the medium are calculated todifferent retention times of the sample.

Another technique that may be employed is liquid chromatography, whichis a separation technique in which the mobile phase is a liquid. Liquidchromatography can be carried out either in a column or a plane. Liquidchromatography that generally utilizes very small packing particles anda relatively high pressure is referred to as high performance liquidchromatography (HPLC). In the HPLC technique, the sample is forcedthrough a column that is packed with irregularly or spherically shapedparticles or a porous monolithic layer (stationary phase) by a liquid(mobile phase) at high pressure. HPLC is generally divided into twodifferent sub-classes based on the polarity of the mobile and stationaryphases. The technique in which the stationary phase is more polar thanthe mobile phase is called normal phase liquid chromatography (NPLC) andthe opposite is called reversed phase liquid chromatography (RPLC).Reversed-phase chromatography is an elution procedure used in liquidchromatography in which the mobile phase is significantly more polarthan the stationary phase. The appropriate method and conditions ofchromatography to separate the mixtures of 4- and 5-substitutedregioisomers are well known in the art.

Polymers of the invention may be used in a wide variety of compositionssuch as in adhesives, agricultural, biocides, coatings, electronics,household-industrial-institutional (HI&I), inks, membranes, metalfluids, oilfield, paper, paints, plastics, printing, plasters, andwood-care compositions.

Compositions belonging to the personal care/cosmetic and pharmaceuticalarts find utility in altering, delivering an active, enhancing,improving, modifying the appearance, condition, color, health, style ofthe skin (including face, scalp, and lips), hair, nails, and oralcavity. Many examples and product forms of these compositions are known.These compositions can impart benefits that include, but are not limitedto, hair style flexibility, hair style durability, humidity resistancefor hair, color and/or color protection, moisturization, wrinklereduction, protection from ultraviolet radiation, water proofness, waterresistance, wear resistance, thermal protection, adhesion, activeingredient delivery, anti-cavity, and/or anti-gingivitis protection. Assuch, these compositions are sometimes categorized in the followingareas: skin care, hair care (both styling and non-styling), sun care,cosmetics (including color cosmetics), antiperspirants, deodorants, oralhygiene, and men's and women's personal hygiene/grooming. In some casesthese benefits and care areas overlap with another.

Skin care compositions include those materials used on the body, face,hands, lips, and/or scalp, and are beneficial for many reasons, such asfirming, anti-cellulite, moisturizing, nourishing, cleaning, reducing oreliminating the appearance of wrinkles or lentigo, toning, and/orpurifying. They also can be used to sanitize.

Consumers can identify many of the compositions that serve the sun carearea, for example after-fun, children's, beach, self-tan, sports (i.e.,being sweatproof, waterproof, resistant to running, or having added UVabsorbers and/or antioxidants), sensitive skin products (i.e., havinglow irritation to the eyes and/or skin, and/or being free of fragrancesand/or dyes), daily wear, leave-on hair creams, lotions, stylingproducts, and hair sprays. Typically, sun care products also compriseone or more UV actives, which are those organic and inorganic materialsthat scatter, absorb, and/or reflect radiation having a wavelength fromabout 100 nm to about 400 nm. In one aspect, the sun care productprotects against UV-A and/or UV-B radiation. UV-A radiation, from about320 nm to about 400 nm, has the longest wavelength within the UVspectrum, and consequently is the least energetic. While UV-A rays caninduce skin tanning, they are liable to induce adverse changes as well,especially in the case of sensitive skin or of skin, which iscontinually exposed to solar radiation. In particular UV-A rays cause aloss of skin elasticity and the appearance of wrinkles, leading topremature skin aging. UV-B rays have shorter wavelengths, from about 290nm to about 320 nm, and their higher energy can cause erythema and skinburns, which may be harmful. Alternatively, sun care products may omitUV actives, and may be regarded as a tanning oil or a tan promoter. Somesun care compositions may promote soothe skin after sun exposure, and/orbe formulated for application to the lips, hair, or the area around theeyes. Self-tan compositions, which are products that color skin withoutrequiring full sun exposure, also fit under the sun care umbrella. Themany different sun care product formats include may assume a consistencyranging from liquid to semiliquid forms (e.g., milks, creams), tothicker forms like gels, creams, pastes, and even solid- and wax-likeforms. Sun care products also may take the form of an aerosol, spray,mist, roll-on, or wipe.

Hair care compositions include shampoos, leave-on and rinse-outconditioners used for conditioning, moisturizing, repairing, haircolors, hair relaxers, and deep conditioners and treatments such as hotoils and waxes, 2-in-1 shampoo/conditioner combination products, 3-in-1shampoo/conditioner/styling agent. The many types of hair care productscan be delivered in an array of formats, including aerosol sprays, pumpsprays, gel sprays, mousses, gels, waxes, creams, pomades, spritzes,putties, lacquers, de-frizzing serums, perms, relaxants and colorants.

Color cosmetic compositions include facial make-up, eye makeup,mascaras, lip and nail products. Facial make-up compositions includefoundation (liquid, solid, and semi-solid)—skin tinted creams, liquid,sticks, mousses used as a base under make-up, rouge, face powder,blusher, highlighters, face bronzers, concealers, and 2-way cakeproducts.

Personal care/cosmetics also include eye make-up, mascaras, eyeliners,eye shadows, eyebrow pencils and eye pencils. Lip products includelipsticks, lip pencils, lip gloss, transparent bases and tinted lipmoisturizers as well as multi-function color sticks that can also beused for cheeks and eyes. Nail products include nail varnishes/enamels,nail varnish removers, treatments, home-manicure products such ascuticle softeners and nail strengtheners.

In addition to the skin, hair, and sun care compositions summarizedabove, the polymers related herein also find application in oral carecompositions. Non-limiting examples or oral care compositions includetoothpastes (including toothpaste gels), denture adhesives, whiteners,anesthetics, and dental floss and related products. These compositionsmay take any product format, such as pastes, gels, creams, solutions,dispersions, rinses, flosses, aerosols, powders, and lozenges.

Grooming products for men and women include shaving products andtoiletries, which may find use in preparing the skin and/or hair for dryor wet shaving. In addition, these compositions may help to moisturize,cool, and/or soothe skin. A variety of product forms are known, a few ofwhich are foams, gels, creams, sticks, oils, solutions, tonics, balms,aerosols, mists, sprays, and wipes.

The polymer can also be used in other personal care/cosmeticapplications, such as an absorbent material in appropriate applicationssuch as diapers, incontinence products, feminine products, and otherrelated products.

The polymers described herein also find application in bath and showercompositions, such as foams, gels, salts, oils, balls, liquids, powdersand pearls. Also included are bar soaps, body washes, shower gels,cleansers, gels, oils, foams, scrubs and creams. As a natural extensionof this category, these compositions also include liquid soaps and handsanitizers used for cleaning hands.

The polymer of the invention can be used in combination with one or moreadditional personal care/cosmetically acceptable additives chosen from,for example, conditioning agents, protecting agents, such as, forexample, hydrosoluble, liposoluble and water-insoluble UV filters,antiradical agents, antioxidants, vitamins and provitamins, fixingagents, oxidizing agents, reducing agents, dyes, cleansing agents,anionic, cationic, nonionic and amphoteric surfactants, thickeners,perfumes, pearlizing agents, stabilizers, pH adjusters, filters,preservatives, hydroxy acids, various cationic, anionic and nonionicpolymers, cationic and nonionic polyether associative polyurethanes,vegetable oils, mineral oils, synthetic oils, polyols such as glycolsand glycerol, silicones, aliphatic alcohols, colorants, bleachingagents, highlighting agents and sequestrants.

For some embodiments, it may be preferred to add one or morepreservatives and/or antimicrobial agents, such as, but not limited to,benzoic acid, sorbic acid, dehydroacetic acid, piroctone olamine, DMDMhydantoin, IPBC, triclosan, bronopol, formaldehyde, isothiazolinones,nitrates/nitrites, parabens, phenoxyethanol, potassium sorbate, sodiumbenzoate, sulphites, and sulphur dioxide. Combinations of preservativesmay be used.

In other embodiments it may be desirable to incorporate preservativeboosters/solvents, select examples of which include caprylyl glycol,hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamicacid, and glyceryl caprylate. Humectants, which include glycerin,butylene glycol, propylene glycol, sorbitol, mannitol, and xylitol maybe added. Polysaccharides, such as gum Arabic, may be included as well.It may be desirable to include one or more other ingredients, such asthose described in U.S. patent publication 2010/0183532 and WO2010/105050, which disclosures are incorporated herein by reference.

These additives may be present in the composition according to theinvention in proportions that may range from about 0% to about 20% byweight in relation to the total weight of the composition. The preciseamount of each additive may be easily determined by an expert in thefield according to its nature and its function.

Examples of these co-ingredients and many others can be found in thefollowing references, each of which is herein incorporated in itsentirety by reference: “Inventory and common nomenclature of ingredientsemployed in cosmetic products,” Official Journal of the European Union,5.4.2006, pages L 97/1 through L 97/528; and International CosmeticIngredient Dictionary and Handbook, 13^(th) edition, ISBN: 1882621476,published by The Personal Care Products Council in January 2010.

Any known conditioning agent is useful in the personal care/cosmeticcompositions of this invention. Conditioning agents function to improvethe cosmetic properties of the hair, particularly softness, thickening,untangling, feel, and static electricity and may be in liquid,semi-solid, or solid form such as oils, waxes, or gums. Similarly, anyknown skin-altering agent is useful in the compositions of thisinvention. A few examples of conditioning agents include cationicpolymers, cationic surfactants and cationic silicones. Conditioningagents may be chosen from synthesis oils, mineral oils, vegetable oils,fluorinated or perfluorinated oils, natural or synthetic waxes,silicones, cationic polymers, proteins and hydrolyzed proteins, ceramidetype compounds, cationic surfactants, fatty amines, fatty acids andtheir derivatives, as well as mixtures of these different compounds.

The synthesis oils include polyolefins, e.g., poly-α-olefins such aspolybutenes, polyisobutenes and polydecenes. The polyolefins can behydrogenated. The mineral oils suitable for use in the compositions ofthe invention include hexadecane and oil of paraffin. Suitable animaland vegetable oils include sunflower, corn, soy, avocado, jojoba,squash, raisin seed, sesame seed, walnut oils, fish oils, glyceroltricaprocaprylate, Purcellin oil or liquid jojoba. Suitable natural orsynthetic oils include eucalyptus, lavender, vetiver, litsea cubeba,lemon, sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon,hyssop, caraway, orange, geranium, cade, and bergamot. Suitable naturaland synthetic waxes include carnauba wax, candelila wax, alfa wax,paraffin wax, ozokerite wax, vegetable waxes such as olive wax, ricewax, hydrogenated jojoba wax, absolute flower waxes such as blackcurrant flower wax, animal waxes such as bees wax, modified bees wax(cerabellina), marine waxes and polyolefin waxes such as polyethylenewax.

The cationic polymers that may be used as a conditioning agent accordingto the invention are those known to improve the cosmetic properties ofhair treated by detergent compositions. The expression “cationicpolymer” as used herein, indicates any polymer containing cationicgroups and/or ionizable groups in cationic groups. The cationic polymersused generally have a molecular weight the average number of which fallsbetween about 500 and 5,000,000, for example between 1000 and 3,000,000.Cationic polymers may be chosen from among those containing unitsincluding primary, secondary, tertiary, and/or quaternary amine groupsthat may either form part of the main polymer chain or a side chain.Useful cationic polymers include known polyamine, polyaminoamide, andquaternary polyammonium types of polymers, such as:

-   -   (1) homopolymers and copolymers derived from acrylic or        methacrylic esters or amides. The copolymers can contain one or        more units derived from acrylamides, methacrylamides, diacetone        acrylamides, acrylamides and methacrylamides, acrylic or        methacrylic acids or their esters, vinyllactams such as vinyl        pyrrolidone or vinyl caprolactam, and vinyl esters. Specific        examples include: copolymers of acrylamide and dimethyl amino        ethyl methacrylate quaternized with dimethyl sulfate or with an        alkyl halide; copolymers of acrylamide and methacryloyl oxyethyl        trimethyl ammonium chloride; the copolymer of acrylamide and        methacryloyl oxyethyl trimethyl ammonium methosulfate;        copolymers of vinyl pyrrolidone/dialkylaminoalkyl acrylate or        methacrylate, optionally quaternized, such as the products sold        under the name Gafquat® by International Specialty Products; the        dimethyl amino ethyl methacrylate/vinyl caprolactam/vinyl        pyrrolidone terpolymers, such as the product sold under the name        Gaffix® VC 713 by International Specialty Products; the vinyl        pyrrolidone/methacrylamidopropyl dimethyl amine copolymer,        marketed under the name Styleze® CC-10 by International        Specialty Products; the vinyl pyrrolidone/quaternized dimethyl        amino propyl methacrylamide copolymers such as the product sold        under the name Gafquat® HS-100 by International Specialty        Products; and the vinyl pyrrolidone/dimethylaminopropyl        methacrylamide/C₉-C₂₄ alkyldimethylaminopropyl methacrylic acid        quaternized terpolymers described in U.S. Pat. No. 6,207,778 and        marketed under the name Styleze® W-20 by International Specialty        Products.    -   (2) derivatives of cellulose ethers containing quaternary        ammonium groups, such as hydroxy ethyl cellulose quaternary        ammonium that has reacted with an epoxide substituted by a        trimethyl ammonium group.    -   (3) derivatives of cationic cellulose such as cellulose        copolymers or derivatives of cellulose grafted with a        hydrosoluble quaternary ammonium monomer, as described in U.S.        Pat. No. 4,131,576, such as the hydroxy alkyl cellulose, and the        hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulose grafted        with a salt of methacryloyl ethyl trimethyl ammonium,        methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl        ammonium.    -   (4) cationic polysaccharides such as described in U.S. Pat. Nos.        3,589,578 and 4,031,307, guar gums containing cationic trialkyl        ammonium groups and guar gums modified by a salt, e.g., chloride        of 2,3-epoxy propyl trimethyl ammonium.    -   (5) polymers composed of piperazinyl units and alkylene or        hydroxy alkylene divalent radicals with straight or branched        chains, possibly interrupted by atoms of oxygen, sulfur,        nitrogen, or by aromatic or heterocyclic cycles, as well as the        products of the oxidation and/or quaternization of such        polymers.    -   (6) water-soluble polyamino amides prepared by polycondensation        of an acid compound with a polyamine. These polyamino amides may        be reticulated.    -   (7) derivatives of polyamino amides resulting from the        condensation of polyalkylene polyamines with polycarboxylic        acids followed by alkylation by bi-functional agents.    -   (8) polymers obtained by reaction of a polyalkylene polyamine        containing two primary amine groups and at least one secondary        amine group with a dioxycarboxylic acid chosen from among        diglycolic acid and saturated dicarboxylic aliphatic acids        having 3 to 8 atoms of carbon. Such polymers are described in        U.S. Pat. Nos. 3,227,615 and 2,961,347.    -   (9) the cyclopolymers of alkyl dialyl amine or dialkyl diallyl        ammonium such as the homopolymer of dimethyl diallyl ammonium        chloride and copolymers of diallyl dimethyl ammonium chloride        and acrylamide.    -   (10) quaternary diammonium polymers such as hexadimethrine        chloride. Polymers of this type are described particularly in        U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547,        3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432,        3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627,        4,025,653, 4,026,945, and 4,027,020.    -   (11) quaternary polyammonium polymers, including, for example,        Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175        products sold by Miranol.    -   (12) the quaternary polymers of vinyl pyrrolidone and vinyl        imidazole such as the products sold under the names Luviquat® FC        905, FC 550, and FC 370 by BASF.    -   (13) quaternary polyamines.    -   (14) reticulated polymers known in the art.

Other cationic polymers that may be used within the context of theinvention are cationic proteins or hydrolyzed cationic proteins,polyalkyleneimines such as polyethyleneimines, polymers containing vinylpyridine or vinyl pyridinium units, condensates of polyamines andepichlorhydrins, quaternary polyurethanes, and derivatives of chitin. Inone aspect, the cationic polymers may be derivatives of quaternarycellulose ethers, the homopolymers and copolymers of dimethyl diallylammonium chloride, quaternary polymers of vinyl pyrrolidone and vinylimidazole, and mixtures thereof.

The conditioning agent can be any silicone known by those skilled in theart to be useful as a conditioning agent. The silicones suitable for useaccording to the invention include polyorganosiloxanes that areinsoluble in the composition. The silicones may be present in the formof oils, waxes, polymers, or gums. They may be volatile or non-volatile.The silicones can be selected from polyalkyl siloxanes, polyarylsiloxanes, polyalkyl aryl siloxanes, silicone gums and polymers, andpolyorgano siloxanes modified by organofunctional groups, and mixturesthereof. Suitable polyalkyl siloxanes include polydimethyl siloxaneswith terminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C₁-C₂₀) siloxanes. Suitable polyalkyl arylsiloxanes include polydimethyl methyl phenyl siloxanes and polydimethyldiphenyl siloxanes, linear or branched. The silicone gums suitable foruse herein include polydiorganosiloxanes including those having anumber-average molecular weight between 200,000 and 1,000,000, usedalone or mixed with a solvent. Examples include polymethyl siloxane,polydimethyl siloxane/methyl vinyl siloxane gums, polydimethylsiloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methyl siloxaneand polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane.Suitable silicone polymers include silicones with a dimethyl/trimethylsiloxane structure and polymers of the trimethyl siloxysilicate type.The organo-modified silicones suitable for use in the invention includesilicones such as those previously defined and containing one or moreorganofunctional groups attached by means of a hydrocarbon radical andgrafted siliconated polymers. In one embodiment the silicones are aminofunctional silicones. The silicones may be used in the form ofemulsions, nano-emulsions, or micro-emulsions.

The conditioning agent can be a protein or hydrolyzed cationic ornon-cationic protein. Examples of these compounds include hydrolyzedcollagens having triethyl ammonium groups, hydrolyzed collagens havingtrimethyl ammonium and trimethyl stearyl ammonium chloride groups,hydrolyzed animal proteins having trimethyl benzyl ammonium groups(benzyltrimonium hydrolyzed animal protein), hydrolyzed proteins havinggroups of quaternary ammonium on the polypeptide chain, including atleast one C₁-C₁₈ alkyl. Hydrolyzed proteins include Croquat™ L, in whichthe quaternary ammonium groups include a C₁₂ alkyl group, Croquat™ M, inwhich the quaternary ammonium groups include C₁₀-C₁₈ alkyl groups,Croquat™ S in which the quaternary ammonium groups include a C₁₈ alkylgroup and Crotein Q in which the quaternary ammonium groups include atleast one C₁-C₁₈ alkyl group. These products are sold by Croda. Theconditioning agent can comprise quaternized vegetable proteins such aswheat, corn, or soy proteins such as cocodimonium hydrolyzed wheatprotein, laurdimonium hydrolyzed wheat protein and steardimoniumhydrolyzed wheat protein.

The conditioning agent can be a ceramide type of compound such as aceramide, a glycoceramide, a pseudoceramide, or a neoceramide. Thesecompounds can be natural or synthetic. Compounds of the ceramide typeare, for example, described in Patents pending DE4424530, DE4424533,DE4402929, DE4420736, WO95/23807, WO94/07844, EP-A-0646572, WO95/16665,FR-2 673 179, EP-A-0227994, WO 94/07844, WO 94/24097, and WO 94/10131.Ceramide type compounds useful herein include 2-N-linoleoylamino-octadecane-1,3-diol, 2-N-oleoyl amino-octadecane-1,3-diol,2-N-palmitoyl amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3-diol, 2-N-behenoyl amino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, N-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl N-cetyl) malonamide,N(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl)amide of cetylic acid,N-docosanoyl N-methyl-D-glucamine and mixtures of such compounds.

The conditioning agent can be a cationic surfactant such as a salt of aprimary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimadazoline, or an amine oxide. Suitable examples include mono-, di-, ortri-alkyl quaternary ammonium compounds with a counter-ion such as achloride, methosulfate, tosylate, etc. including, but not limited to,cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and the like. The presence of a quaternary ammoniumcompound in conjunction with the polymer described above reduces staticand enhances combing of hair in the dry state. The polymer also enhancesthe deposition of the quaternary ammonium compound onto the hairsubstrate thus enhancing the conditioning effect of hair.

The conditioning agent can be any fatty amine known to be useful as aconditioning agent; e.g. dodecyl, cetyl or stearyl amines, such asstearamidopropyl dimethylamine. The conditioning agent can be a fattyacid or derivatives thereof known to be useful as conditioning agents.Suitable fatty acids include myristic acid, palmitic acid, stearic acid,behenic acid, oleic acid, linoleic acid, and isostearic acid. Thederivatives of fatty acids include carboxylic ester acids includingmono-, di-, tri- and tetra-carboxylic acids.

The conditioning agent can be a fluorinated or perfluorinated oil.Fluorinated oils include perfluoropolyethers described in EP-A-486135and the fluorohydrocarbon compounds described in WO 93/11103. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons, such asperfluorodecahydronaphthalene, fluoroesters, and fluoroethers. Ofcourse, mixtures of two or more conditioning agents can be used.

The conditioning agent or agents can be present in an amount from about0.001% to about 20%, particularly from about 0.01% to about 10%, andeven more particularly from about 0.1% to about 3% by weight based onthe total weight of the final composition. The personal care/cosmeticcompositions of the invention can contain one or more protecting agentsin combination with the above-described polymer to prevent or limit thedegrading effects of natural physical and/or chemical assaults on thekeratinous materials.

The protecting agent can be chosen from hydrosoluble, liposoluble andwater-insoluble UV filters, antiradical agents, antioxidants, vitaminsand pro-vitamins. The above-described cationic polymer enhances thedeposition of these materials onto the hair or skin substrate enhancingprotection of hair to UV damage. Organic UV filters (systems that filterout UV rays) can be chosen from among hydrosoluble or liposolublefilters, whether siliconated or nonsiliconated, and mineral oxideparticles, the surface of which may be treated. Hydrosoluble organic UVfilters may be chosen from para-amino benzoic acid and its salts,anthranilic acid and its salts, salicylic acid and its salts, hydroxycinnamic acid and its salts, sulfonic derivatives of benzothiazoles,benzimidizoles, benzoxazoles and their salts, sulfonic derivatives ofbenzophenone and their salts, sulfonic derivatives of benzylidenecamphor and their salts, derivatives of benzylidene camphor substitutedby a quaternary amine and their salts, derivatives ofphthalydene-camphosulfonic acids and their salts, sulfonic derivativesof benzotriazole, and mixtures thereof. Hydrophilic polymers, which havelight-protective qualities against UV rays, can be used. These includepolymers containing benzylidene camphor and/or benzotriazole groups.

Suitable liposoluble organic UV filters include derivatives ofpara-aminobenzoic acid, such as the esters or amides ofpara-aminobenzoic acid; derivatives of salicylic acid; derivatives ofbenzophenone; derivatives of dibenzoyl methane; derivatives of diphenylacrylates; derivatives of benzofurans; UV filter polymers containing oneor more silico-organic residues; esters of cinnamic acid; derivatives ofcamphor; derivatives of trianilino-s-triazine; the ethylic esterurocanic acid; benzotriazoles; derivatives of hydroxy phenyl triazine;bis-resorcinol-dialkyl amino triazine; and mixtures thereof. Theliposoluble (or lipophilic) organic UV filter can be chosen from octylsalicylate; 4-tert-butyl-4′-methoxy dibenzoyl methane; octocrylene;4-methoxy cinnamate; 2-ethylhexyl [2-ethylhexyl 4-methoxycinnamate]; and2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsily)oxy]disiloxanyl]propynyl]phenol. Other UV filters that may beuseful are derivatives of benzophenones such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxy benzophenone,derivatives of benzalmalonates such as polydimethyl/methyl(3(4-(2,2-bis-ethoxy carbonyl vinyl)-phenoxy)-propenyl)siloxane, derivatives of benzylidene camphor such as b-b′ camphosulfonic[1-4 divinylbenzene] acid and derivatives of benzimidazole such as2-phenyl-benzimidazol-5-sulfonic acid. Water-insoluble UV filtersinclude various mineral oxides. The mineral oxides may be selected fromamong titanium oxides, zinc oxides, and cerium oxides. The mineraloxides can be used in the form of ultrafine nanoparticles. For example,the UV filters can include Escalol® HP-610 (dimethylpabamido propyllaurdimonium tosylate and propylene glycol stearate) or Crodasorb HP(polyquaternium 59).

The antioxidants or antiradical agents can be selected from phenols suchas BHA (tert-butyl-4-hydroxy anisole), BHT (2,6-di-tert-butyl-p-cresol),TBHQ (tert-butyl hydroquinone), polyphenols such as proanthocyanodicoligomers, flavonoids, hindered amines such as tetra amino piperidine,erythorbic acid, polyamines such as spermine, cysteine, glutathione,superoxide dismutase, and lactoferrin.

The vitamins can be selected from ascorbic acid (vitamin C), vitamin E,vitamin E acetate, vitamin E phosphate, B vitamins such as B3 and B5,vitamin PP, vitamin A, and derivatives thereof. The provitamins can beselected from panthenol and retinol.

The protecting agent can be present in an amount from about 0.001% toabout 20% by weight, particularly from about 0.01% to about 10% byweight, and more particularly from 0.1% to about 5% by weight of thetotal weight of the final composition.

The composition of the invention can contain a fixing agent incombination with the above-described polymer. The fixing agent can be ananionic polymer chosen from polymers containing carboxylic units derivedfrom unsaturated carboxylic mono- or polyacids of the formula:

in which n is a whole number from 0 to 10, A₁ denotes a methylene group,optionally bonded to the carbon atom of the unsaturated group or to aneighboring methylene group when n is greater than 1 by means of aheteroatom like oxygen or sulfur, R₇ denotes a hydrogen atom, a phenylor benzyl group, R₈ denotes a hydrogen atom, a lower alkyl or carboxylgroup, R₉ denotes a hydrogen atom, a lower alkyl group, a —CH₂—COOH,phenyl or benzyl group and polymers containing units derived fromsulfonic acid like vinylsulfonic, styrenesulfonic,acrylamidoalkylsulfonic units.

The fixing agent can be an amphoteric polymer chosen from the polymercontaining recurring units derived from:

-   -   a) at least one monomer chosen from acrylamides or        methacrylamides substituted on the nitrogen with an alkyl        radical,    -   b) at least one acid copolymer containing one or more reactive        carboxyl groups, and    -   c) at least one basic comonomer, such as esters with primary,        secondary, tertiary, and quaternary amino substituents of        acrylic and methacrylic acids and the product of quaternization        of dimethylaminoethyl methacrylate with dimethyl or diethyl        sulfate.

The fixing agent can be a nonionic polymer chosen frompolyalkyloxazolines; vinyl acetate homopolymers; vinyl acetate andacrylic ester copolymers; vinyl acetate and ethylene copolymers; vinylacetate and maleic ester copolymers; polyethylene and maleic anhydridecopolymers; homopolymers of alkyl acrylates; homopolymers of alkylmethacrylates; copolymers of acrylic esters; copolymers of alkylacrylates and alkyl methacrylates; copolymers of acrylonitrile and anonionic monomer chosen from among butadiene and alkyl(meth)acrylates;copolymers of alkyl acrylate and urethane; and polyamides. The fixingagent can be a functionalized or unfunctionalized, silicone ornon-silicone polyurethane. The fixing polymer can be a polymer of thegrafted silicone type containing a polysiloxane portion and a portionconsisting of a nonsilicone organic chain, with one of the two portionsforming the main chain of the polymer, and with the other being graftedonto said main chain.

The fixing agent can be present in the composition in a relative weightconcentration between about 0.1% to about 10%, for example, from about0.5% to about 5%.

The personal care/cosmetic composition of the invention can contain anoxidizing agent in combination with the above-described polymer. Theoxidizing agent can be chosen from the group of hydrogen peroxide, ureaperoxide, alkali metal bromates, ferricyanides, persalts, and redoxenzymes, optionally with their respective donor or cofactor. Forexample, the oxidizing agent can be hydrogen peroxide. The oxidizingagent can be a solution of oxygenated water whose titer varies from 1 to40 volumes.

The personal care/cosmetic composition of the invention can contain atleast one reducing agent in combination with the above-described polymerin amounts from about 0.01% to about 30%, particularly from about 0.05%to about 20% of the total weight of the composition. The reducing agentscan be selected from thiols, like cysteine, thioglycolic acid,thiolactic acid, their salts and esters, cysteamine, and its salts orsulfites. In the case of compositions intended for bleaching, ascorbicacid, its salts and its esters, erythorbic acid, its salts and itsesters, and sulfinates, like sodium hydroxymethanesulfinate can be used.

The personal care/cosmetic composition of the invention can contain adye in combination with the above-described polymer. The dye can beselected from the group consisting of neutral acid or cationicnitrobenzene dyes, neutral acid or cationic azo dyes, quinone dyes,neutral, acid or cationic anthraquinone dyes, azine dyes, triarylmethanedyes, indoamine dyes and natural dyes. The dye or dyes can be present ina concentration from about 0.001% to about 20%, and particularly fromabout 0.005% to about 10% based on the total weight of the composition.

The personal care/cosmetic composition of the invention can contain atleast one amphoteric polymer or a cationic polymer in combination withthe above-described polymer. Suitable cationic polymers include apoly(quaternary ammonium) consisting of recurrent units corresponding tothe following formulae (W) and (U):

Suitable amphoteric polymers include a copolymer containing at least oneacrylic acid and a dimethyldiallyammonium salt as a monomer. Thecationic or amphoteric polymer or polymers can be present in an amountfrom about 0.01% to about 10%, particularly from about 0.05% to about5%, and more particularly from about 0.1% to about 3% by weight of thetotal weight of the composition.

In addition, the personal care/cosmetic compositions can include atleast one surfactant in combination with the above-described polymer.The surfactant can be present in an amount from about 0.1% to about 60%,particularly from about 1% to about 40%, and more particularly fromabout 5% to about 30% by weight based on the total weight of thecomposition. The surfactant may be chosen from among anionic,amphoteric, or non-ionic surfactants, or mixtures of them known to beuseful in personal care/cosmetic compositions.

One or more suitable thickeners or viscosity increasing agents may beincluded in combination with the above-described polymer in the personalcare/cosmetic compositions of the invention. Suitable thickeners and/orviscosity increasing agents include: Acetamide MEA;Acrylamide/Ethalkonium Chloride Acrylate Copolymer;Acrylamide/Ethyltrimonium Chloride Acrylate/Ethalkonium ChlorideAcrylate Copolymer; Acrylamides Copolymer; Acrylamide/Sodium AcrylateCopolymer; Acrylamide/Sodium Acryloyldimethyltaurate Copolymer;Acrylates/Acetoacetoxyethyl Methacrylate Copolymer;Acrylates/Beheneth-25 Methacrylate Copolymer; Acrylates/C10-30 AlkylAcrylate Crosspolymer; Acrylates/Ceteth-20 Itaconate Copolymer;Acrylates/Ceteth-20 Methacrylate Copolymer; Acrylates/Laureth-25Methacrylate Copolymer; Acrylates/Palmeth-25 Acrylate Copolymer;Acrylates/Palmeth-25 Itaconate Copolymer; Acrylates/Steareth-50 AcrylateCopolymer; Acrylates/Steareth-20 Itaconate Copolymer;Acrylates/Steareth-20 Methacrylate Copolymer; Acrylates/StearylMethacrylate Copolymer; Acrylates/Vinyl Isodecanoate Crosspolymer;Acrylic Acid/Acrylonitrogens Copolymer; Adipic Acid/Methyl DEACrosspolymer; Agar; Agarose; Alcaligenes Polysaccharides; Algin; AlginicAcid; Almondamide DEA; Almondamidopropyl Betaine; Aluminum/MagnesiumHydroxide Stearate; Ammonium Acrylates/Acrylonitrogens Copolymer;Ammonium Acrylates Copolymer; Ammonium Acryloyldimethyltaurate/VinylFormamide Copolymer; Ammonium Acryloyldimethyltaurate/VP Copolymer;Ammonium Alginate, Ammonium Chloride; Ammonium PolyacryloyldimethylTaurate; Ammonium Sulfate; Amylopectin; Apricotamide DEA;Apricotamidopropyl Betaine; Arachidyl Alcohol; Arachidyl Glycol; ArachisHypogaea (Peanut) Flour; Ascorbyl Methylsilanol Pectinate; AstragalusGummifer Gum; Attapulgite; Avena Sativa (Oat) Kernel Flour; AvocadamideDEA; Avocadamidopropyl Betaine, Azelamide MEA; Babassuamide DEA;Babassuamide MEA; Babassuamidopropyl Betaine; Behenamide DEA; BehenamideMEA, Behenamidopropyl Betaine; Behenyl Betaine; Bentonite; ButoxyChitosan, Caesalpinia Spinosa Gum; Calcium Alginate; CalciumCarboxymethyl Cellulose; Calcium Carrageenan; Calcium Chloride; CalciumPotassium Carbomer; Calcium Starch Octenylsuccinate; C20-40 AlkylStearate; Canolamidopropyl Betaine; Capramide DEA;Capryl/Capramidopropyl Betaine; Carbomer; Carboxybutyl Chitosan;Carboxymethyl Cellulose Acetate Butyrate; Carboxymethyl Chitin;Carboxymethyl Chitosan; Carboxymethyl Dextran; CarboxymethylHydroxyethylcellulose; Carboxymethyl Hydroxypropyl Guar; Carnitine;Cellulose Acetate Propionate Carboxylate; Cellulose Gum; CeratoniaSiliqua Gum; Cetearyl Alcohol; Cetyl Alcohol; Cetyl Babassuate; CetylBetaine; Cetyl Glycol; Cetyl Hydroxyethylcellulose; Chimyl Alcohol;Cholesterol/HDI/Pullulan Copolymer; Cholesteryl Hexyl DicarbamatePullulan; Citrus Aurantium Dulcis (Orange) Peel Extract; Cocamide DEA;Cocamide MEA; Cocamide MIPA; Cocamidoethyl Betaine; CocamidopropylBetaine; Cocamidopropyl Hydroxysultaine; Coco-Betaine;Coco-Hydroxysultaine; Coconut Alcohol; Coco/Oleamidopropyl Betaine;Coco-Sultaine; Cocoyl Sarcosinamide DEA; Cornamide/Cocamide DEA;Cornamide DEA; Croscarmellose; Crosslinked Bacillus/Glucose/SodiumGlutamate Ferment; Cyamopsis Tetragonoloba (Guar) Gum; Decyl Alcohol;Decyl Betaine; Dehydroxanthan Gum; Dextrin; Dibenzylidene Sorbitol;Diethanolaminooleamide DEA; Diglycol/CHDM/Isophthalates/SIP Copolymer;Dihydroabietyl Behenate; Dihydrogenated Tallow Benzylmonium Hectorite;Dihydroxyaluminum Aminoacetate; Dimethicone/PEG-10 Crosspolymer;Dimethicone/PEG-15 Crosspolymer; Dimethicone Propyl PG-Betaine;Dimethylacrylamide/Acrylic Acid/Polystyrene Ethyl MethacrylateCopolymer; Dimethylacrylamide/Sodium AcryloyldimethyltaurateCrosspolymer; Disteareth-100 IPDI; DMAPA Acrylates/AcrylicAcid/Acrylonitrogens Copolymer; Erucamidopropyl Hydroxysultaine;Ethylene/Sodium Acrylate Copolymer; Gelatin; Gellan Gum; GlycerylAlginate; Glycine Soja (Soybean) Flour; Guar HydroxypropyltrimoniumChloride; Hectorite; Hyaluronic Acid; Hydrated Silica; HydrogenatedPotato Starch; Hydrogenated Tallow; Hydrogenated Tallowamide DEA;Hydrogenated Tallow Betaine; Hydroxybutyl Methylcellulose; HydroxyethylAcrylate/Sodium Acryloyldimethyl Taurate Copolymer;Hydroxyethylcellulose; Hydroxyethyl Chitosan; HydroxyethylEthylcellulose; Hydroxyethyl Stearamide-MIPA;Hydroxylauryl/Hydroxymyristyl Betaine; Hydroxypropylcellulose;Hydroxypropyl Chitosan; Hydroxypropyl Ethylenediamine Carbomer;Hydroxypropyl Guar; Hydroxypropyl Methylcellulose; HydroxypropylMethylcellulose Stearoxy Ether; Hydroxypropyl Starch; HydroxypropylStarch Phosphate; Hydroxypropyl Xanthan Gum; Hydroxystearamide MEA;Isobutylene/Sodium Maleate Copolymer; Isostearamide DEA; IsostearamideMEA; Isostearamide MIPA; Isostearamidopropyl Betaine; Lactamide MEA;Lanolinamide DEA; Lauramide DEA; Lauramide MEA; Lauramide MIPA;Lauramide/Myristamide DEA; Lauramidopropyl Betaine; LauramidopropylHydroxysultaine; Laurimino Bispropanediol; Lauryl Alcohol; LaurylBetaine; Lauryl Hydroxysultaine; Lauryl/Myristyl Glycol HydroxypropylEther; Lauryl Sultaine; Lecithinamide DEA; Linoleamide DEA; LinoleamideMEA; Linoleamide MIPA; Lithium Magnesium Silicate; Lithium MagnesiumSodium Silicate; Macrocystis Pyrifera (Kelp); Magnesium Alginate;Magnesium/Aluminum/Hydroxide/Carbonate; Magnesium Aluminum Silicate;Magnesium Silicate; Magnesium Trisilicate; Methoxy PEG-22/Dodecyl GlycolCopolymer; Methylcellulose; Methyl Ethylcellulose; MethylHydroxyethylcellulose; Microcrystalline Cellulose; MilkamidopropylBetaine; Minkamide DEA; Minkamidopropyl Betaine; MIPA-Myristate;Montmorillonite; Moroccan Lava Clay; Myristamide DEA; Myristamide MEA;Myristamide MIPA; Myristamidopropyl Betaine; MyristamidopropylHydroxysultaine; Myristyl Alcohol; Myristyl Betaine; Natto Gum;Nonoxynyl Hydroxyethylcellulose; Oatamide MEA; Oatamidopropyl Betaine;Octacosanyl Glycol Isostearate; Octadecene/MA Copolymer; Oleamide DEA;Oleamide MEA; Oleamide MIPA; Oleamidopropyl Betaine; OleamidopropylHydroxysultaine; Oleyl Betaine; Olivamide DEA; Olivamidopropyl Betaine;Oliveamide MEA; Palmamide DEA; Palmamide MEA; Palmamide MIPA;Palmamidopropyl Betaine; Palmitamide DEA; Palmitamide MEA;Palmitamidopropyl Betaine; Palm Kernel Alcohol; Palm Kernelamide DEA;Palm Kernelamide MEA; Palm Kernelamide MIPA; Palm KernelamidopropylBetaine; Peanutamide MEA; Peanutamide MIPA; Pectin; PEG-800;PEG-Crosspolymer; PEG-150/Decyl Alcohol/SMDI Copolymer; PEG-175Diisostearate; PEG-190 Distearate; PEG-15 Glyceryl Tristearate; PEG-140Glyceryl Tristearate; PEG-240/HDI Copolymer Bis-Decyltetradeceth-20Ether; PEG-100/IPDI Copolymer; PEG-180/Laureth-50/TMMG Copolymer;PEG-10/Lauryl Dimethicone Crosspolymer; PEG-15/Lauryl DimethiconeCrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 Methyl Glucose Trioleate; PEG-180/Octoxynol-40/TMMG Copolymer;PEG-150 Pentaerythrityl Tetrastearate; PEG-4 Rapeseedamide;PEG-150/Stearyl Alcohol/SMDI Copolymer; Phaseolus Angularis Seed Powder;Polianthes Tuberosa Extract; Polyacrylate-3; Polyacrylic Acid;Polycyclopentadiene; Polyether-1; Polyethylene/Isopropyl Maleate/MACopolyol; Polyglyceryl-3 Disiloxane Dimethicone; Polyglyceryl-3Polydimethylsiloxyethyl Dimethicone; Polymethacrylic Acid;Polyquaternium-52; Polyvinyl Alcohol; Potassium Alginate; PotassiumAluminum Polyacrylate; Potassium Carbomer; Potassium Carrageenan;Potassium Chloride; Potassium Palmate; Potassium Polyacrylate; PotassiumSulfate; Potato Starch Modified; PPG-2 Cocamide; PPG-1 HydroxyethylCaprylamide; PPG-2 Hydroxyethyl Cocamide; PPG-2 HydroxyethylCoco/Isostearamide; PPG-3 Hydroxyethyl Soyamide; PPG-14 Laureth-60 HexylDicarbamate; PPG-14 Laureth-60 Isophoryl Dicarbamate; PPG-14 Palmeth-60Hexyl Dicarbamate; Propylene Glycol Alginate; PVP/Decene Copolymer; PVPMontmorillonite; Pyrus Cydonia Seed; Pyrus Malus (Apple) Fiber;Rhizobian Gum; Ricebranamide DEA; Ricinoleamide DEA; Ricinoleamide MEA;Ricinoleamide MIPA; Ricinoleamidopropyl Betaine; Ricinoleic Acid/AdipicAcid/AEEA Copolymer; Rosa Multiflora Flower Wax; Sclerotium Gum;Sesamide DEA; Sesamidopropyl Betaine; Sodium Acrylate/AcryloyldimethylTaurate Copolymer; Sodium Acrylates/Acrolein Copolymer; SodiumAcrylates/Acrylonitrogens Copolymer; Sodium Acrylates Copolymer; SodiumAcrylates Crosspolymer; Sodium Acrylate/Sodium AcrylamidomethylpropaneSulfonate Copolymer; Sodium Acrylates/Vinyl Isodecanoate Crosspolymer;Sodium Acrylate/Vinyl Alcohol Copolymer; Sodium Carbomer; SodiumCarboxymethyl Chitin; Sodium Carboxymethyl Dextran; Sodium CarboxymethylBeta-Glucan; Sodium Carboxymethyl Starch; Sodium Carrageenan; SodiumCellulose Sulfate; Sodium Chloride; Sodium Cyclodextrin Sulfate; SodiumHydroxypropyl Starch Phosphate; Sodium Isooctylene/MA Copolymer; SodiumMagnesium Fluorosilicate; Sodium Oleate; Sodium Palmitate; Sodium PalmKernelate; Sodium Polyacrylate; Sodium Polyacrylate Starch; SodiumPolyacryloyldimethyl Taurate; Sodium Polygamma-Glutamate; SodiumPolymethacrylate; Sodium Polystyrene Sulfonate; Sodium Silicoaluminate;Sodium Starch Octenylsuccinate; Sodium Stearate; Sodium StearoxyPG-Hydroxyethylcellulose Sulfonate; Sodium Styrene/Acrylates Copolymer;Sodium Sulfate; Sodium Tallowate; Sodium Tauride Acrylates/AcrylicAcid/Acrylonitrogens Copolymer; Sodium Tocopheryl Phosphate; SolanumTuberosum (Potato) Starch; Soyamide DEA; Soyamidopropyl Betaine;Starch/Acrylates/Acrylamide Copolymer; Starch HydroxypropyltrimoniumChloride; Stearamide AMP; Stearamide DEA; Stearamide DEA-Distearate;Stearamide DIBA-Stearate; Stearamide MEA; Stearamide MEA-Stearate;Stearamide MIPA; Stearamidopropyl Betaine; Steareth-60 Cetyl Ether;Steareth-100/PEG-136/HDI Copolymer; Stearyl Alcohol; Stearyl Betaine;Sterculia Urens Gum; Synthetic Fluorphlogopite; Tallamide DEA; TallowAlcohol; Tallowamide DEA; Tallowamide MEA; Tallowamidopropyl Betaine;Tallowamidopropyl Hydroxysultaine; Tallowamine Oxide; Tallow Betaine;Tallow Dihydroxyethyl Betaine; Tamarindus Indica Seed Gum; TapiocaStarch; TEA-Alginate; TEA-Carbomer; TEA-Hydrochloride; Trideceth-2Carboxamide MEA; Tridecyl Alcohol; Triethylene Glycol Dibenzoate;Trimethyl Pentanol Hydroxyethyl Ether; Triticum Vulgare (Wheat) GermPowder; Triticum Vulgare (Wheat) Kernel Flour; Triticum Vulgare (Wheat)Starch; Tromethamine Acrylates/Acrylonitrogens Copolymer; TromethamineMagnesium Aluminum Silicate; Undecyl Alcohol; Undecylenamide DEA;Undecylenamide MEA; Undecylenamidopropyl Betaine; Welan Gum; WheatGermamide DEA; Wheat Germamidopropyl Betaine; Xanthan Gum; YeastBeta-Glucan; Yeast Polysaccharides and Zea Mays (Corn) Starch.

In one such embodiment, the thickeners or viscosity increasing agentsinclude carbomers, Aculyn™ and Stabileze®, e.g., crosslinked acrylicacid, crosslinked poly(methylvinyl ether/maleic anhydride) copolymer,acrylamides, carboxymethyl cellulose, and the like.

The personal care/cosmetic compositions may be used to wash and treatkeratinous material such as hair, skin, eyelashes, eyebrows,fingernails, lips, and hairy skin.

The personal care/cosmetic compositions can be detergent compositionssuch as shampoos, bath gels, and bubble baths. In this mode, thecompositions will comprise a generally aqueous washing base. Thesurfactant or surfactants that form the washing base may be chosen aloneor in blends, from known anionic, amphoteric, or non-ionic surfactants.The quantity and quality of the washing base must be sufficient toimpart a satisfactory foaming and/or detergent value to the finalcomposition. The washing base can be from about 4% to about 50% byweight, particularly from about 6% to about 35% by weight, and even moreparticularly from about 8% to about 25% by weight of the total weight ofthe final composition.

The pH of the composition applied to the keratinous material isgenerally between 2 and 12. In one embodiment, the pH is from about 3 toabout 8, and may be adjusted to the desired value by means of acidifyingor alkalinizing agents that are well known in the state of the art.Thus, the composition of the invention can contain at least onealkalizing or acidifying agent in amounts from about 0.01% to about 30%based on the total weight of the composition.

The alkalizing agent can be chosen from ammonia, alkali carbonates,alkanolamines, like mono-, di- and triethanolamines, as well as theirderivatives, hydroxyalkylamines and ethoxylated and/or propoxylatedethylenediamines, sodium or potassium hydroxides and compounds of thefollowing formula:

in which R is a propylene residue optionally substituted with anhydroxyl group or a C₁-C₄ alkyl radical; R₃₈, R₃₉, R₄₀ and R₄₁,identical or different, represent a hydrogen atom, a C₁-C₄ alkyl radicalor C₁-C₄ hydroxyalkyl radical.

The acidifying agent can be chosen from mineral or organic acids, likehydrochloric acid, orthophosphoric acid, carboxylic acids like tartaricacid, citric acid, or lactic acid, or sulfonic acids, and the like.

The personal care/cosmetic compositions of the invention may include aphysiological and cosmetically acceptable medium. Such medium mayconsist exclusively of water, a cosmetically acceptable solvent, or ablend of water and a cosmetically acceptable solvent, such as a loweralcohol composed of C₁ to C₄, such as ethanol, isopropanol, t-butanol,n-butanol, alkylene glycols such as propylene glycol, and glycol ethers.Alternatively, the personal care/cosmetic compositions can be anhydrous.

Generally, personal care/cosmetic compositions can be prepared by simplemixing procedures well known in the art. The invention provides a methodfor treating keratinous material including the skin or hair, by applyingto skin or keratinous materials a personal care/cosmetic composition asdescribed above, and then eventually rinsing it with water. Accordingly,the method makes it possible to maintain the hairstyle, treatment, care,washing, or make-up removal of the skin, the hair, and any otherkeratinous material. The personal care/cosmetic compositions may alsotake the form of after-shampoo compositions, to be rinsed off or not,for permanents, straightening, waving, dyeing, or bleaching, or the formof rinse compositions to be applied before or after dyeing, bleaching,permanents, straightening, relaxing, waving or even between the twostages of a permanent or straightening process. The personalcare/cosmetic compositions may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products. The personalcare/cosmetic compositions may also be in the form of aqueous orhydro-alcoholic solutions for skin and/or hair care. The personalcare/cosmetic compositions described herein are useful in personalcare/cosmetic products, including, but not limited to, gels, lotions,glazes, glues, mousses, sprays, fixatives, shampoos, conditioners,2-in-1 shampoos, temporary hair dyes, semi-permanent hair dyes,permanent hair dyes, straighteners, permanent waves, relaxers, creams,putties, waxes, pomades, moisturizers, mascaras, lip balms and foamenhancers.

The modified polymers can be prepared according to the examples set outbelow. The examples are presented for purposes of demonstrating, but notlimiting, the preparation of the compounds and compositions of thisinvention.

EXAMPLES

The following non-limiting examples are provided to illustrate a few ofthe methods for preparing novel 4- and 5-substituted 1,2,3-triazoles,and regioisomer mixtures thereof, modified polymers.

Example 1

A 2-L, 4-neck, round-bottom flask was equipped with a mechanical mixer,thermometer, condenser, air purge and a hot oil bath with temperatureprobe and controller. An air purge was maintained. Sodium azide (100grams) and water (490 grams) were charged to the flask. The azide wasfully dissolved before adding the amine (221 grams). The amine was alsofully dissolved in the aqueous solution. The solution turned hazy orangewith this addition. The oil bath was preheated to 100° C. Propargylalcohol (15.67 grams) was added at t=0. The reaction flask was placed inthe hot oil bath with mixing. At reflux, the reaction became a clearorange solution. Refluxing was maintained for 25 hours. All during thereaction, air flowed through the flask as a purge. The reactiontemperature at reflux was maintained at 102° C.-103° C., even with theair purge. Over the first hour of refluxing, the reaction solutionchanged from orange to a clear light gold color. Propargyl alcohol(15.67 grams) was added again at 2, 3, 4 and 5 hours from t=0. The colorchanged to clear dark amber after refluxing 25 hours. The reaction wastransferred to a single-neck two liter round bottom flask. Water wasstripped from the reaction solution on the roto-evaporator at 80° C. and30 Torr (final). This resulted in viscous amber oil choked with salt.After cooling, 500 mL of methanol was added to the oil and the mixturewas mechanically mixed for 30 minutes. The oil readily dissolved. Themethanol was stripped-off on the roto-evaporator at 80° C. and 55 Torr(final). A viscous amber oil with solids remained. Methanol (500 mL) wasadded and the mixture was mechanically mixed for 30 minutes. The oilreadily dissolved. The salts were filtered and rinsed with methanol. Themethanol was stripped-off on the roto-evaporator at 80° C. and 55 Torr(final). A viscous and hazy amber oil remained. Methanol (300 mL) wasadded and the mixture was mechanically mixed and chilled in an ice bath.The remaining salts were filtered out and the methanol et al. werestripped off. The resulting product was a viscous amber “tar.” Aquantity of 219 grams was collected representing a 72% yield ofprotonated intermediate. Fifty grams of the intermediate and 250 mL ofethyl acetate were charged to a 1-L, 4-neck, round bottom flask equippedwith mechanical mixer, thermometer and bubbler. The contents were mixedfor 30 minutes and a reaction temperature of 28-31° C. was maintained.Next, KHCO₃ (125 grams) was added to the mixture at t=0 hours and mixingwas continued. At t=4 hours, product was detected via GC. A secondaddition of 125 grams of KHCO₃ was then added. The reaction was mixedovernight and the reaction was a gold-yellow mixture. The mixture wasfiltered to remove salts and the salts were rinsed with ethyl acetate toa total reaction solution volume of 750 mL. At this point, the reactionwas a cloudy yellow solution. Magnesium sulfate (40 grams) was added todehydrate and the mixture was mixed for one hour. The reaction mixturewas filtered and the solution stripped at 80° C. to 30 Torr (final). Theresult was 29 grams (58% yield) of a clear gold deprotonated oilproduct. NMR results confirmed the identity of the product, designatedas compound 1.

Example 2

A 500-mL, round bottom, 4-neck reaction flask equipped with mechanicalstirrer, air supply, oil bath with temperature probe and controller, andreflux condenser was charged with water (103.0 grams). With mixing,sodium azide (25.0 grams, 0.3845 mol), bromooctane (67.49 grams, 0.3495mol) and propargyl alcohol (5.2 grams) were added. The flask was thenpurged continuously with air to sweep hydrazoic acid gas out of theflask as it formed. The purge was maintained during the reaction. Thereaction was heated at reflux for 25 hours within a temperature range of100° C.-104° C. Aliquots of propargyl alcohol were added during thefirst six hours of refluxing. At 2 hours into the reaction, 5.2 gramswere added followed by 5.2 grams each at 3, 4, 5, and 6 hours. At theend of 24 hours of refluxing, the reaction emulsion was transferred to aseparatory funnel. 500 mL of water was added and mixed. Then, 200 mL ofbrine were added to promote phase separation. After 1.5 hours, themixture separated into two phases: a top thick opaque dark gold phaseand a bottom cloudy yellow phase. The bottom aqueous phase wasdiscarded. The top organic phase was charged to a 500-mL, 4-neck, roundbottom flask equipped with a mechanical mixer. Hexane (50 mL) and water(50 mL) were added to the flask and the contents were mixed mechanically(at 500 rpm) for 40 minutes. The resulting emulsion was then transferredback to a separatory funnel where it was left to phase separate. Brine(50 mL) was added to aid in separation. Three phases eventually formed(top=hexane, colorless, middle=product dark, bottom=aqueous cloudyyellow). The top and bottom phases were discarded, and the dark middlelayer was collected. The middle layer was evaporated at 80° C. for 1hour. Three portions of water (10 mL each) were added to the productphase and then stripped off sequentially at 95° C. for 2.5 hours. Theproduct phase was added to a 4-neck, round bottom flask charged with 250mL hexane and mixed well overnight. The hexane layer was decanted off(no product in hexane was detected by GC). The solids were filtered outresulting in phased-out oil/hexane mix (B) and light colored crystals(A). The solids were dissolved in 250 mL of ethyl acetate and theresulting clear gold solution was added to mix (B). The resultingsolution (about 300 mL) was then washed with 300 mL brine by mechanicalmixing in a flask for 30 minutes. The mix phased-separated quickly. Thetop organic phase (ethyl acetate+product) was collected and charged to around bottom flask. Silica gel (70 grams) was added and the mixture wasmixed rigorously for 30 minutes. The mix was filtered resulting in aclear gold solution. The solution was stripped of solvent leaving aclear gold oil. The oil slowly became a soft gold crystalline form,which exhibited two DSC melt points at 17° C. and 37° C. suggesting 1,4and 1,5 triazole isomers. NMR results confirmed the identity of theproduct, designated as compound 2.

Example 3

1.00:0.10, respectively

A quantity of 116.0 grams (0.8287 mol) of poly(methyl vinylether-co-maleic anhydride) polymer (Gantrez® AN-119, InternationalSpecialty Products, Wayne, N.J.) having a nominal molecular weight ofabout 200,000 Da, and 270 mL of ethyl acetate were charged into a 1-L,4-neck, round-bottom flask equipped with a mechanical mixer,thermometer, slow-addition (SA) funnel and bubbler. Mixing was initiatedat moderate speed to form an ivory-white cream having a thickconsistency. Then, 15.0 grams (0.08287 mol) of compound 1 (Example 1)were dissolved in 45 grams of ethyl acetate and charged into the clearamber solution via the SA funnel over 30 minutes at room temperature(25° C.-30° C.). With the addition, the reaction solids changed from athick ivory-white cream to a light-orange slurry. After adding 12% ofthe solution of compound 1, the reaction mixture appeared to coagulate.With further addition to a total of about 18% of 1 solution, thereaction mixture assumed a lower viscosity (“soupy”) having abright-pink color. This appearance and consistency remained through theentire thirty-minute addition and during hold period of one hour. Noexotherm was observed. The reaction was monitored by observing thedisappearance of compound 1 over time (18.76 minutes) via gaschromatography (GC). The reaction was mixed overnight at roomtemperature. The reaction was filtered and a light-pink product filtercake was collected. The filtrate was clear and colorless. The solidswere then rinsed with ethyl acetate, air dried in the exhaust hood andoven-dried at 50° C. under vacuum overnight. The yield for this reactionwas 118 grams of a light pink powder. NMR and FT-IR confirmed thecomposition of this modified polymer.

Example 4

A quantity of 50.0 grams (0.1010 mole) of polymer product from Example 3and 170 mL of distilled water were charged to a 500-mL, 4-neck,round-bottom flask equipped with a mechanical mixer, thermometer andbubbler. These ingredients were mixed at moderate speed to form a pinkmixture having a pH of about 8.5. After a total of 60 minutes of mixing,the reaction had a “slimy” viscous consistency with a pH about around2.0. Relative levels of compound 1 were monitored by gas chromatography(18.76 minutes) during the reaction process to determine the extent oftriazole cleaving from the polymer backbone. The reaction was left tosettle and partition to a clear, pink filtrate over a viscous pink“syrup.” The filtrate was decanted from the syrup (190 mL), which wasthen added to 1 L of vigorously mixing methyl acetate. The syrup wasmixed, dispersed and washed in the methyl acetate for 30 minutes. Themixture was left to partition again and the cloudy light pink liquid wasdecanted off the syrup. The syrup was again mixed in 1 L of methylacetate for 30 minutes. At this point, a change in the property of thehydrolyzed polymer product from Example 3 was noted. This was likely dueto the displacement of water by methyl acetate. Instead of a syrup, thehydrolyzed product now physically resembled a hard pink putty. Thecloudy light pink solvent was decanted from the “putty” solids. Thesolids were collected, air-dried in a hood and then placed under vacuumat room temperature overnight. Yield for this reaction was 48 grams of alight pink powder from 50 grams of starting material. NMR and FT-IRconfirmed the composition of this modified polymer.

Example 5

1.00:0.20, respectively.

A quantity of 58.0 grams (1.0 eq.) of poly(methyl vinyl ether-co-maleicanhydride) polymer (Gantrez® AN-119, International Specialty Products,Wayne, N.J.) having a nominal molecular weight of about 200,000 Da wasdissolved in 120 mL ethyl acetate and charged in to 1-L, 4 neck roundbottom flask equipped with a mechanical mixer, thermometer,slow-addition (SA) funnel and bubbler. Then, 15 grams (0.2 eq.) of themixture of compound 1 was dissolved in 38 grams of ethyl acetate andcharged to the SA funnel. Mixing was initiated at room temperature, andthe mixture of 1 solution was added evenly over a period of thirtyminutes. No exotherm was observed. The appearance/disappearance ofresidual mixture of compound 1 was followed via GC. Mixing continued atmoderate to fast speed for another hour. Then, the product precipitated,which was filtered and washed. This solid was air-dried, followed byoven drying at 60° C. under vacuum overnight. NMR and IR confirmed thecomposition of this modified polymer.

Example 6

1.00:0.30, respectively.

A quantity of 38.7 grams (0.2764 mol) of poly(methyl vinylether-co-maleic anhydride) polymer (Gantrez® AN-119, InternationalSpecialty Products, Wayne, N.J.) having a nominal molecular weight ofabout 200,000 Da, and 89 mL of ethyl acetate were charged in to a 1-L,4-neck, round-bottom flask equipped with a mechanical mixer,thermometer, slow-addition (SA) funnel and bubbler. Mixing was initiatedat moderate speed to an ivory-white cream having a thick consistency.Then, 15.0 grams (0.0829 mol) of compound 2 (Example 2) was dissolved in38 grams of ethyl acetate and this clear amber solution was charged viathe SA funnel over forty minutes at room temperature (25° C.-30° C.).Initially, the reaction solids were a creamy light gold color. However,with 31% of the 2 solution added, the reaction mixture was a loose, pinkslurry. This appearance and consistency remained through the entirethirty-minute addition and a hold period of one hour. No exotherm wasobserved. The reaction was monitored by observing the disappearance of 2over time via gas chromatography (GC). At the end of the hold period,the reaction was filtered. A pink powder cake was collected in thefilter funnel and the hazy yellow filtrate was sampled for GC analysis.The solids were rinsed with ethyl acetate, air dried and then oven-driedat 60° C. under vacuum overnight. The yield for this reaction was 48grams of a very light tan powder. NMR and IR confirmed the compositionof this modified polymer.

Example 7

1.00:0.40, respectively.

A quantity of 60.0 grams (0.4286 mol) of poly(methyl vinylether-co-maleic anhydride) polymer (Gantrez® AN-119, InternationalSpecialty Products, Wayne, N.J.) having a nominal molecular weight ofabout 200,000 Da, and 117 mL of ethyl acetate were charged in to a 1-L,4-neck, round-bottom flask equipped with a mechanical mixer,thermometer, slow-addition (SA) funnel and bubbler. Mixing was initiatedat moderate speed to form an ivory-white cream having a thickconsistency. Then, 31.0 grams (0.1714 mol) of compound 2 were dissolvedin 85 mL of ethyl acetate, and this clear amber solution was charged viathe SA funnel at room temperature (25-30° C.) over forty-five minutes.Initially, the reaction solids looked dry and crumbled with mixing.However, with 11% of 2 solution added, the reaction mixture was a loose,pink slurry. This appearance and consistency remained through the entirethirty-minute addition and a hold period of one hour. No exotherm wasobserved. The reaction was monitored by observing the disappearance of 2over time via gas chromatography (GC). At the end of the hold period,the reaction was filtered. A pink-orange powder cake was collected inthe filter funnel and the clear yellow filtrate was sampled for GCanalysis. The solids were rinsed with ethyl acetate, air dried and thenoven-dried at 60° C. under vacuum overnight. The yield for this reactionwas 79.0 grams of a tan powder. NMR and FTIR confirmed the compositionof this modified polymer.

Example 8

1.00:0.50, respectively.

A quantity of 58.0 grams (0.4143 mol, 1.0 eq.) of poly(methyl vinylether-co-maleic anhydride) polymer (Gantrez® AN-119, InternationalSpecialty Products, Wayne, N.J.) having a nominal molecular weight ofabout 200,000 Da was dissolved in 120 mL of ethyl acetate and charged to1-L, 4-neck, round bottom flask equipped with a mechanical mixer,thermometer, slow-addition (SA) funnel and bubbler. Then, 15 grams (0.2eq., 0.0829 mol) of compound 2 was dissolved in 38 grams of ethylacetate and charged via the SA funnel at room temperature over thirtyminutes. No exotherm was observed. The presence of residual compound 2was followed via GC. Mixing was continued at moderate to fast speed foranother hour. At this point the product precipitated from solution, wasair dried, and then oven dried overnight at 60° C. under vacuum. NMR andIR confirmed the composition of this modified polymer.

Example 9

1.00:1.00, respectively.

A quantity of 58.0 grams (1.0 eq., 0.4143 mol) of poly(methyl vinylether-co-maleic anhydride) polymer (Gantrez® AN-119, InternationalSpecialty Products, Wayne, N.J.) having a nominal molecular weight ofabout 200,000 Da was dissolved in 120 mL of ethyl acetate and charged into 1-L, 4-neck, round bottom flask equipped with a mechanical mixer,thermometer, slow-addition (SA) funnel and bubbler. Then, 75 grams (1.0eq., 0.4143 moles) of compound 2 were dissolved in 38 grams of ethylacetate and charged via the SA funnel at room temperature over thirtyminutes. No exotherm was observed. The presence of residual compound 2was followed via GC. Mixing was continued at moderate to fast speed foranother hour. At this point the product precipitated, which wasfiltered, washed, air dried, and then oven dried overnight at 60° C.under vacuum. NMR and IR confirmed the composition of this modifiedpolymer.

Example 10

A quantity of 116.02 grams (0.8287 mol) of poly(methyl vinylether-co-maleic anhydride) polymer (Gantrez® AN-119, InternationalSpecialty Products, Wayne, N.J.) having a nominal molecular weight ofabout 200,000 Da was charged with 270 mL of ethyl acetate to a 2-L,4-neck, round-bottom flask equipped with a mechanical mixer,thermometer, slow-addition (SA) funnel and bubbler. Mixing was initiatedat moderate speed to an ivory-white cream having a thick consistencyformed. Then, a solution of 13.93 grams of compound 2 (Example 2)dissolved in 30 mL of ethyl acetate was charged to the flask. The colorof the reaction mixture changed to a light gold. Following thisaddition, a solution of compound 1 (Example 1) (3.07 g) dissolved in 45mL of ethyl acetate was charged to the slow-add funnel and slow-addedover 30 minutes at room temperature. During the addition, the appearanceand consistency of the reaction mixture changed. An exotherm was notobserved. During the first 20 minutes, pink granules formed in the lightgold mixture. With 27% of the 1 solution added, the smooth dark tanreaction solids became mealy and then cheesy-looking (lumpy like cottagecheese). However, with all of the 1 solution added, the reaction mixturechanged to a soupy caramel color with dark pink granules. The reactionwas held at room temperature for 1.5 hours with mixing. Ethyl acetate(300 mL) was added 1 hour after the slow-addition. At this point, thereaction mixture was a soupy red color. Mixing was continued for anotherhour at room temperature. The reaction was heated to reflux (62° C.)within 10 minutes. Refluxing was continued for 2 hours. Another 0.02 eq.(3.07 grams) of compound 1 was then added to catalyze the reaction.Refluxing (79° C.) was continued for another hour after the catalystaddition. The reaction became a mixture of red and pink granules and wasleft to mix slowly overnight at room temperature. The following day, thereaction mixture was refluxed at 78° C. with mixing for an additional 5hours. The product was sticky red granules.

The reaction mixture was cooled and mixed hard. A cloudy dark red ethylacetate reaction solution was slowly decanted from mushy dark pinksolids left in the flask. Methyl acetate (1 L) was added to the solidsand the mixture was again mixed hard for 2 hours. Dark red solvent wasthen decanted from dark pink solids remaining in the flask. This time,ethyl acetate (1 L) was added to the solids and the mixture wasthoroughly mixed for 30 minutes. Upon filtering, the filtrate was clearand colorless. The red-pink granular product was collected, air-dried inthe exhaust hood overnight and then dried under vacuum at 25° C. Darkpink granular solids (41 grams) were collected from this reaction. NMRand FT-IR confirmed the composition of this modified polymer, designatedas compound 10.

Example 11

A quantity of 15.0 grams of compound 10 and 55 grams of distilled waterwere charged to a 500 mL, 4-neck, round-bottom flask equipped with amechanical mixer, thermometer and bubbler. Mixing occurred at moderatespeed to form a foamy purple mixture having a pH of about 7.0. After atotal of 60 minutes of mixing, the clear pink reaction solution with apH of about 4.5 was decanted off, leaving a dark pink solidintermediate. Relative levels of 1 and 2 isomers were monitored by gaschromatography (˜18.76 and ˜21.7 minutes, respectively) during thereaction process to determine the extent of triazole cleaving from thepolymer backbone. Methyl acetate (200 mL) was added to the solids andthe reaction was mixed for 20 minutes. At this point, the reactionconsisted of a light purple sediment in a cloudy purple liquid in a 500mL reaction flask. Water (100 mL) was added to the mixture and it wasmixed for one hour. The result was an opaque purple liquid totaling 320mL. The reaction mixture was added to an equivalent volume (320 mL) ofethyl acetate with 15 minutes of mixing. The reaction was now an opaquepink mixture. The reaction was left to settle and partition to a darkred filtrate over pink amorphous “syrup.” The filtrate was decanted fromthe “syrup”. The syrup was placed in a glass dish and air-dried in anexhaust hood. After sufficiently drying, the solids were collected,air-dried in a hood and then placed under vacuum at room temperatureovernight. The yield for this reaction was 11.1 g of a light pink powderfrom 15.0 g from compound 10. NMR and FT-IR confirmed the composition ofthis modified polymer, designated as compound 11.

While a number of embodiments of this invention have been represented,it was apparent that the basic construction can be altered to provideother embodiments that utilize the invention without departing from thespirit and scope of the invention. All such modifications and variationsare intended to be included within the scope of the invention as definedin the appended claims rather than the specific embodiments that havebeen presented by way of example.

We claim:
 1. A 4- or 5-substituted 1,2,3-triazole, or regioisomermixtures thereof, modified polymer, wherein the substituted1,2,3-triazole is modified by a modifying polymer represented by thestructure:

wherein R₁ is selected from the group consisting of hydrogen,functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl,and aryl groups, wherein any of the before mentioned groups may be withor without heteroatoms, and mixtures thereof.
 2. The modified polymeraccording to claim 1, wherein the 4- or 5-substituted 1,2,3-triazole, orregioisomer mixtures thereof, are represented by the structures,respectively:

wherein X is OH or NHR₂; each R₂ is independently selected from thegroup consisting of hydrogen, functionalized and unfunctionalized alkyl,alkoxy, cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof; and each p is an integer independently ranging from 1 to about50.
 3. The modified polymer according to claim 2, wherein R₂ is selectedfrom the group consisting of hydrogen and functionalized andunfunctionalized alkyl and alkoxy groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof; X is OH; and each p is an integer independently ranging from 1to about
 6. 4. The modified polymer according to claim 1, wherein themodified polymer is selected from the group consisting of:

wherein R₁, R₂, and R₃ are each independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,alkoxy, cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms, and mixturesthereof; M₁ is selected from the group consisting of hydrogen, alkalimetals, and alkaline earth metals; M₂ is an alkali metal or an alkalineearth metal; each m, n, and q is an integer independently ranging fromabout 2 to about 500; and each p is an integer independently rangingfrom 1 to about
 50. 5. The modified polymer according to claim 4,wherein R₁, R₂, and R₃ are each independently selected from the groupconsisting of hydrogen and functionalized and unfunctionalized alkyl andalkoxy groups, wherein any of the before mentioned groups may be with orwithout heteroatoms, and mixtures thereof; X is OH; and each p is aninteger independently ranging from 1 to about
 6. 6. The modified polymeraccording to claim 4, wherein the modified polymer is represented by thestructure:


7. The mixture according to claim 4, wherein the modified polymer isrepresented by the structure:


8. The modified polymer according to claim 4, wherein the modifiedpolymer is represented by the structure:


9. The modified polymer according to claim 4, wherein the modifiedpolymer is represented by the structure:


10. The modified polymer according to claim 4, wherein the modifiedpolymer is represented by the structure: